1. Field of the Invention
The invention relates to a disinfectant. More particularly, it relates to a series of water-insoluble polymeric quaternary phosphonium salts used for bactericides in which a resin is used as a carrier.
2. Discussion of the Prior Art
Development of water-insoluble polymeric bactericides has been started on in order to overcome the drawbacks such as, for example, high poison, easily foaming etc., of water-soluble bactericides, in U.S. Pat. No. 4,349,646, a water-insoluble polymeric quaternary ammonium salt type of bactericide having different structures is prepared by reacting a chloromethyl-containing resin (such as a chloromthylated and crosslinked or uncrosslinked polystyrene resin or a polychloromethyl-acrylate resin) with tertiary amine, di-tertiary-group diamine. In U.S. Pat. No. 4,826,924, a nitrogen-containing polymer type of bactericide is prepared by reacting a chloromethyl-containing polystyrene or polystyrene-divinylbenzene resin with a bipyridinonium having a long chain alkyl or a tert-amino quaternary ammonium salt. In the application of CN 97,116726.5, the inventors of the present invention describes that an amphoteric polymer type of batericide has been prepared by carrying an amino acid-type surfactant on a chloromethylated polystyrene-divinyl benzene resin.
The above-listed bactericides are all the water-insoluble nitrogen-containing bactericide. In recent years, along with the deepening of the study of a water-soluble quaternary ammonium salt type bactericide and a water-soluble quaternary phosphonium salt type bactericide, it has been found that the bactericidal activity of the quaternary phosphonium type bactericides is higher than that of the quaternary ammonium salt type bactericides with similar structures. Thus, it can be assumed that if a water-insoluble polymeric quaternary phosphonium type bactericide is prepared by carrying a quaternary phosphonium salt having batericidal activity on a resin, much higher bacteridical effect will be expectantly obtained. However, it is difficult to carry a quaternary phosphonium salt on a resin technically. At present there are some reports in this area in the world. Akihiko describes a method for synthesizing a polymeric quaternary phosphonium salt in "Polymeric Phosphonium Salts as a Novel Class of Cationic Biocides. X." (cf. Journal of Applied Polymer Science, Vol. 54, 1305-1310, 1994), that is to say, by firstly carrying out the quaterisation of a long chain of tertiary phosphine with chloromethyl styrene, and then polymerizing the resulting product, i. e. carrying the active groups on the resin prior to the polymerization. Although the polymeric quaternary phosphonium salt obtained by this method has highly effective and rapid bactericidal effect, there are some defects as below: (1) the starting materials are not easy to obtain, the chloromethyl styrene and tertiary phosphine used by the authors are not available as commercial products, and the conditions of reaction when prepared in laboratory are very stricted: (2) it is very difficult to increase the degree of polymerization by using the method of carrying active groups prior to the polymerization, thus the product obtained still has a certain content of solubility in water.
JP 5310820 reports that an insoluble polymeric quaternary phosphonium salt is prepared by carrying a quaternary phosphonium salt-type bactericide on a polymer carrier through the electrostatic effect between the anionic ion, such as --SO.sub.3 --, of the polymer and the cationic ion of the quaternary phosphonium salt. But, the most important defect of the polymeric quaternary phosphonium salt obtained by this method is that the combination between the quaternary phosphonium salt, which is carried on the resin only by the electrostatic effect between anionic ion and cationic ion, and such a combination is not strong enough, so that the bactericide can be easily stripped from the resin into aqueous phase while treated by using water, thereby resulting in environmental pollution.
An object of the present invention is to provide a novel water-insoluble polymeric quaternary phosphonium salt type bactericide series in order to overcome the drawbacks of the prior art. The bactericide series of the present invention not only has a rapid and highly effective bactericidal activity, but also can be used repeatedly.